On possible spin injection at non-ideal Schottky contacts

The role of the tunneling mechanisms in metal-disordered layer-semiconductor structure under spin injection at the interface is investigated. The non-ideal metal-semiconductor structure as prepared by ionized cluster beam deposition is considered, and it is shown that the depletion region of the semiconductor can be tailored to include a suitably heavily doped region near the interface. The tunneling is described within a simplified model in which the expression for the interface resistance of the metal-disordered layer-semiconductor structure is obtained. It is argued that in the case of ionized cluster beam deposited non-ideal Schottky structure a significant spin injection is achieved.     

Real time ellipsometry for monitoring plasma-assisted epitaxial growth of GaN

GaN is grown on Si-face 4H-SiC(0 0 0 1) substrates using remote plasma-assisted methods including metalorganic chemical vapour deposition (RP-MOCVD) and molecular beam epitaxy (MBE). Real time spectroscopic ellipsometry is used for monitoring all the steps of substrate pre-treatments and the heteroepitaxial growth of GaN on SiC. Our characterization emphasis is on understanding the nucleation mechanism and the GaN growth mode, which depend on the SiC surface preparation.     

Synthesis of poly(p‐phenylene sulfide) from bis(4‐bromophenyl) disulfide

Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006     

Synthesis and characterization of poly(arylene ether)s containing 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one or 6‐(4‐hydroxyphenyl)pyridazine moieties

A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (T_g's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The T_g's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed T_g's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐T_g polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006     

Determination of Taxotere in human plasma by a semi-automated high-performance liquid chromatographic method.

A rapid, selective and reproducible high-performance liquid chromatographic (HPLC) method with ultraviolet detection was developed for the determination of the anti-cancer agent Taxotere in biological fluids. The method involves a solid-phase extraction step (C2 ethyl microcolumns) using a Varian Advanced Automated Sample Processor (AASP) followed by reversed-phase HPLC. The validated quantitation range of the method is 10-2500 ng/ml in plasma with coefficients of variation < or = 11%. The method is also suitable for the determination of Taxotere in urine samples under the same conditions. The method was applied in a phase I tolerance study of Taxotere in cancer patients, allowing the pharmacokinetic profile of Taxotere to be established.     

Oligonucleotide Analogues with Integrated Bases and Backbone. Part 14

The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl₃/(D₆)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation.     

Characterisation of raw materials for production of ceramics

The aim of this paper is to characterize some raw materials used for ceramics material production. Five samples of clay have been analyzed. It has been carried out a patterned sampling in a quarry in Rosarno (South Italy). Chemical-physical properties on clay samples are determined. Test pieces have been prepared and physical properties after firing are determined by DSC thermal analysis, XRD analysis and X-ray fluorescence. It is important to note the high amount of Fe₂O₃. The mixture principally contains quartz, illite and oligoclase. It has been observed the colour and the shape after firing: predominant colour is red. In this case the clay has been used in mixtures covered with glazes. The colour of internal clay is hidden by opaque of glazes. The analysed raw materials can be used in a slip for single fired red tiles. The A2sp clay produces best ceramics at 1000°C.     

Facile synthesis of exfoliated and highly conductive poly(arylene disulfide)/graphite nanocomposites

Exfoliated graphite has been synthesized by first synthesizing H₂SO₄ intercalated compound in a H₂O₂‐H₂SO₄ mixture, followed by exfoliation under microwave irradiation. Poly(arylene disulfide)/graphite nanocomposites were then fabricated by absorbing cyclic(arylene disulfide) oligomers into the pores of exfoliated graphite. Subsequently, the nanocomposite precursor was subjected to heat treatment to carry out the in situ ring‐opening polymerization of the oligomers via free radical mechanism. The as‐prepared nanocomposite exhibited a exfoliated nanostructure as evidenced by transmission electron microscopy (TEM) observation. The nanocomposite with a very small amount of graphite, 5 wt%, possesses a highly electrical conductivity of 4 S/cm, therefore, many applications can be found as conductive materials. Copyright © 2004 John Wiley & Sons, Ltd.     

Kinetics and mechanism of the acid-catalysed decarboxylation of thecis-α- andcis-β-carbonato(3,6-dimethyl-1,8-diamino-3,6-diazaoctane)-cobalt(III) ions

Summary The acid-catalysed decarboxylation of thecis-- andcis--[CoL(CO₃)]⁺ complexes (L = 3,6-dimethyl-1,8-diamino-3,6-diazaoctane) have been studied over a range of HClO₄ concentrations and the temperatures 25, 35 and 45° at I = 1.0 mol dm^–3 (NaClO₄). The rate expression takes the form k_obs = k₀ + k₁[H⁺] where k_obs is the observed first order rate constant at constant hydrogen ion concentration. The k₀ term makes only a minor contribution to the overall reaction. Both complexes display solvent deuterium isotope effects ofca. 2.6 for the acid-catalysed decarboxylation, consistent with a rapid proton pre-equilibrium mechanism. Activation parameters have been determined and the mechanism of the reaction discussed. The magnitude of the solvent isotope effect is consistent with an A-1 type mechanism involving formation of a 5-coordinate intermediate.